CN109799680A - Chemical amplification positive photosensitive resin composition and its application - Google Patents

Chemical amplification positive photosensitive resin composition and its application Download PDF

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CN109799680A
CN109799680A CN201811343915.7A CN201811343915A CN109799680A CN 109799680 A CN109799680 A CN 109799680A CN 201811343915 A CN201811343915 A CN 201811343915A CN 109799680 A CN109799680 A CN 109799680A
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weight
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methyl
acid
resin composition
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CN109799680B (en
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刘骐铭
黄伟杰
施俊安
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Chi Mei Corp
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Chi Mei Corp
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Abstract

The present invention provides the manufacturing method of a kind of chemical amplification positive photosensitive resin composition, the manufacturing method of substrate with mold and electroplating formation body.Chemical amplification positive photosensitive resin composition includes resin (A), novolac resin (B), photoacid generator (C) and solvent (D), wherein resin (A) includes resin (A-1) and resin (A-2), resin (A-1) is to be reacted by the first mixture and obtained, first mixture includes monomer (a-1-1) and monomer (a-1-2), and monomer (a-1-1) contains the structure such as formula (a-1-1a): monomer (a-1-2) contains cyclic ether group.Resin (A-2) is to be reacted by the second mixture and obtained, and the second mixture includes monomer (a-2-1), and monomer (a-2-1) stretches alkyl chain containing polyoxy.Chemical amplification positive photosensitive resin composition has good sensitivity, and it is formed by photoresist pattern with good rectangularity.

Description

Chemical amplification positive photosensitive resin composition and its application
Technical field
A kind of manufacture of substrate the invention relates to chemical amplification positive photosensitive resin composition, with mold The manufacturing method of method and electroplating formation body, and in particular to a kind of photoresist pattern that can be used to form good rectangularity The good chemical amplification positive photosensitive resin composition of sensitivity, by above-mentioned chemical amplification positive photosensitive resin composition The manufacturing method of substrate obtained with mold, and the manufacture of the electroplating formation body as made from the above-mentioned substrate with mold Method.
Background technique
Now, photoelectricity processing has become the mainstream of precise fine processing technology.Alleged " photoelectricity processing ", refers to and forms photoresist Object is coated on machined object surface and forms photoresist layer, is patterned photoresist layer using photolithographic techniques, then with patterned Photoresist layer (photoresist pattern) be that mask carries out chemical etching, electrolytic etching or electrical forming etc. based on being electroplated, to manufacture The general name of the technology of the various precision components such as semiconductor package body.
Also, in recent years, with the miniaturization of electronic equipment, the high density packaging technique progress of semiconductor package body is quick, And seek the spininess foot film assemblingization of packaging body, package body sizes miniaturization, adopt rewinding method two-dimentional package technique, three Tie up the promotion of the packing density of package technique.In such high density packaging technique, such as: it will be for connecting towards prominent on packaging body The projected electrode (assembling terminal) of convex block etc., the wiring again and assembling terminal that extend from the surrounding terminals on wafer metal column Deng being configured to high precision on substrate, using as connection terminal.
If above-mentioned photoelectricity processing is using light resistance composition, as such light resistance composition, both having known has comprising acid generation The chemical amplification type light resistance composition of agent (referring now to patent document 1,2 etc.).Chemical amplification type light resistance composition is by radiation Line irradiates (exposure) and generates acid by acid producing agent, promotes the diffusion of acid by heat treatment, with the matrix resin in constituent Etc. causing sour catalyst to react, and change its alkali-solubility person.
Such chemical amplification positive light resistance composition is to be used in the electricity such as the convex block or metal column of adopting coating step Plate the formation etc. of formed body.Specifically, being formed on the supports such as metal substrate using chemical amplification type light resistance composition The photoresist layer of desired film thickness is exposed across set mask pattern, images, and forms the photoresist figure used as template Case, wherein being optionally removed (removing) predetermined part that form convex block or metal column.Thereafter, by plating in the removal Partially in (non-photoresist portion) after the conductor of embedment copper etc., then surrounding photoresist pattern is removed, convex block or metal column can be formed.
However, amplification positive photosensitive resin composition documented by above-mentioned, sensitivity and it is formed by photoresist pattern Rectangularity can not be received by dealer.Therefore, it is good and the good photoresist pattern of rectangularity can be formed how to provide a kind of sensitivity Chemical amplification positive light resistance composition, actually current those skilled in the art want to solve the problems, such as.
Summary of the invention
Therefore, an aspect of the invention provides a kind of chemical amplification positive photosensitive resin composition, improves sense Spend and be formed by the rectangularity of photoresist pattern.
Another aspect of the invention provides a kind of manufacturing method of substrate with mold, is increased using chemistry above-mentioned Width type positive-type photosensitive resin composition, is made the mold to form electroplating formation body.
Another aspect of the invention provides a kind of manufacturing method of electroplating formation body, to the substrate for having aforementioned mold It is electroplated, to form electroplating formation body in mold.
Above-mentioned aspect according to the present invention provides a kind of chemical amplification positive photosensitive resin composition first, until Less include resin (A), novolac resin (B), photoacid generator (C) and solvent (D), following division it.
Resin (A)
Resin (A) of the invention includes resin (A-1) and resin (A-2).
Resin (A-1)
Resin (A-1) of the invention is to be reacted by one first mixture and obtained, which includes monomer (a-1-1) And monomer (a-1-2).In one embodiment, monomer (a-1-1) includes the construction such as following formula (a-1-1a):
In formula (a-1-1a), R1aFor hydrogen atom or methyl, R2aFor low alkyl group and X3aWith the carbon atom being bonded The hydrocarbon ring of carbon number 5 to 20 is collectively formed.
In above formula (a-1-1a), R2aThe low alkyl group of expression is straight-chain or branched, R2aFor example, methyl, ethyl, The group of n- propyl, isopropyl, n- butyl, isobutyl group, the second butyl, third butyl, various amyls etc..If reaching high comparison The advantage of degree, high-res, the depth of focus etc., and be preferable with the low alkyl group that carbon number is 2 to 4.
Furthermore X3aThe hydrocarbon ring of mononuclear type or polycyclic type that carbon number is 5 to 20 is formed with the carbon atom being bonded.Mononuclear type hydrocarbon Ring may be, for example, pentamethylene, hexamethylene, cycloheptane, cyclooctane etc..Polycyclic type hydrocarbon ring may be, for example, two ring-like hydrocarbon rings, tricyclic hydrocarbon Ring, four ring-like hydrocarbon rings etc..Specifically, polycyclic type hydrocarbon ring may be, for example, adamantane, norbornane, isoborneol alkane, tristane, Tetracyclododecane etc..In above-mentioned X3aIt is formed in the example for the hydrocarbon ring that carbon number is 5 to 20 with the carbon atom being bonded, and with hexamethylene Alkane ring and adamantane ring are preferable.
The specific example of monomer (a-1-1) can be such as following formula (a-1-1b) to formula (a-1-1g) compound represented.
Monomer (a-1-1) can single use or mixing two kinds it is used above.
Total usage amount based on the first mixture is 100 parts by weight, and the content of monomer (a-1-1) is 10 parts by weight to 50 weights Part is measured, preferably 10 parts by weight to 45 parts by weight, more preferably 10 parts by weight to 40 parts by weight are more preferably.
As unused monomer (a-1-1), the sensitivity of chemical amplification positive photosensitive resin composition is bad and institute's shape At photoresist pattern rectangularity it is poor.
Monomer (a-1-2) of the invention contains cyclic ether group, can enumerate (methyl) Glycidyl Acrylate, (methyl) third Olefin(e) acid -2- methyl polyglycidyl, (methyl) acrylic acid -3,4- epoxy butyl ester, (methyl) acrylic acid -6,7- epoxy heptyl ester, (first Base) acrylic acid -3,4- epoxy cyclohexyl or (methyl) acrylic acid -3,4- epoxycyclohexanecarboxylate etc. three-membered ring's class；3- (first Base) acryloyloxymethyl propylene oxide (3- [(meth) acryloyloxymethyl] oxetane), 3- (methyl) acryloyl-oxy Methyl -3- ethyl propylene oxide, 3- (methyl) acryloyloxymethyl -2- methyloxetane, 3- (methyl) acryloyloxymethyl - 2- trifluoromethyl propylene oxide, 3- (methyl) acryloyloxymethyl -2- pentafluoroethyl group propylene oxide, 3- (methyl) acryloyl-oxy first Base -2- phenyl propylene oxide, 3- (methyl) acryloyloxymethyl -2,2- difluoro propylene oxide, 3- (methyl) acryloyloxymethyl - 2,2,4- trifluoro-epoxy propanes, 3- (methyl) acryloyloxymethyl -2,2,4,4- tetrafluoro propylene oxide, 3- (methyl) acryloyl-oxy Ethyl propylene oxide, 3- (methyl) acrylyl oxy-ethyl -3- ethyl propylene oxide, 2- ethyl -3- (methyl) acrylyl oxy-ethyl Propylene oxide, 3- (methyl) acrylyl oxy-ethyl -2- trifluoromethyl propylene oxide, five fluorine of 3- (methyl) acrylyl oxy-ethyl -2- Ethyl propylene oxide, 3- (methyl) acrylyl oxy-ethyl -2- phenyl propylene oxide, 2,2- bis- fluoro- 3- (methyl) acryloyl-oxy second Basic ring Ethylene Oxide, 3- (methyl) acrylyl oxy-ethyl -2,2,4- trifluoro-epoxy propane, 3- (methyl) acrylyl oxy-ethyl -2,2, 4,4- tetrafluoro propylene oxide, 2- (methyl) acryloyloxymethyl propylene oxide, 2- methyl -2- (methyl) acryloyloxymethyl epoxy Propane, 3- methyl -2- (methyl) acryloyloxymethyl propylene oxide, 4- methyl -2- (methyl) acryloyloxymethyl propylene oxide, 2- (methyl) acryloyloxymethyl -2- trifluoromethyl propylene oxide, 2- (methyl) acryloyloxymethyl -3- trifluoromethyl epoxy third Alkane, 2- (methyl) acryloyloxymethyl -4- trifluoromethyl propylene oxide, 2- (methyl) acryloyloxymethyl -2- pentafluoroethyl group ring Ethylene Oxide, 2- (methyl) acryloyloxymethyl -3- pentafluoroethyl group propylene oxide, five fluorine second of 2- (methyl) acryloyloxymethyl -4- Basic ring Ethylene Oxide, 2- (methyl) acryloyloxymethyl -2- phenyl propylene oxide, 2- (methyl) acryloyloxymethyl -3- benzyl ring Ethylene Oxide, 2- (methyl) acryloyloxymethyl -4- phenyl propylene oxide, 2,3- bis- fluoro- 2- (methyl) acryloyloxymethyl epoxy Propane, 2,4-, bis- fluoro- 2- (methyl) acryloyloxymethyl propylene oxide, 3,3- bis- fluoro- 2- (methyl) acryloyloxymethyl epoxy Propane, 2,4-, bis- fluoro- 2- (methyl) acryloyloxymethyl propylene oxide, 3,4- bis- fluoro- 2- (methyl) acryloyloxymethyl epoxy Propane, 4,4-, bis- fluoro- 2- (methyl) acryloyloxymethyl propylene oxide, 2- (methyl) acryloyloxymethyl -3,3,4- trifluoro ring Ethylene Oxide, 2- (methyl) acryloyloxymethyl -3,4,4- trifluoro-epoxy propane, 2- (methyl) acryloyloxymethyl -3,3,4,4- Tetrafluoro propylene oxide, 2- (methyl) acrylyl oxy-ethyl propylene oxide, 2- (methyl) acrylyl oxy-ethyl -2- methyl epoxy third Alkane, 2- (methyl) acrylyl oxy-ethyl -4- methyloxetane, 2- (methyl) acrylyl oxy-ethyl -2- trifluoromethyl epoxy third Alkane, 2- (methyl) acrylyl oxy-ethyl -3- trifluoromethyl propylene oxide, 2- (methyl) acrylyl oxy-ethyl -4- fluoroform basic ring Ethylene Oxide, 2- (methyl) acrylyl oxy-ethyl -2- pentafluoroethyl group propylene oxide, five fluorine second of 2- (methyl) acrylyl oxy-ethyl -3- Basic ring Ethylene Oxide, 2- (methyl) acrylyl oxy-ethyl -4- pentafluoroethyl group propylene oxide, 2- (methyl) acrylyl oxy-ethyl -2- benzene Basic ring Ethylene Oxide, 2- (methyl) acrylyl oxy-ethyl -3- phenyl propylene oxide, 2- (methyl) acrylyl oxy-ethyl -4- benzyl ring Ethylene Oxide, 2,3-, bis- fluoro- 2- (methyl) acrylyl oxy-ethyl propylene oxide, 2,4- bis- fluoro- 2- (methyl) acrylyl oxy-ethyl ring Ethylene Oxide, 3,3-, bis- fluoro- 2- (methyl) acrylyl oxy-ethyl propylene oxide, 3,4- bis- fluoro- 2- (methyl) acrylyl oxy-ethyl ring Ethylene Oxide, 4,4-, bis- fluoro- 2- (methyl) acrylyl oxy-ethyl propylene oxide, 2- (methyl) acrylyl oxy-ethyl -3,3,4- trifluoro Propylene oxide, 2- (methyl) acrylyl oxy-ethyl -3,4,4- trifluoro-epoxy propane, 2- (methyl) acrylyl oxy-ethyl -3,3,4, Four membered ring's class of 4- tetrafluoro propylene oxide etc.；(methyl) acrylic acid tetrahydrofuran ester, (methyl) acrylic acid modified through caprolactone Tetrahydrofuran ester, (the amyl- 4- yl of 2- methyl -2- isobutyl group -1,3- dioxy ring) methyl (methyl) acrylate ((2-methyl-2- Isobutyl-1,3-dioxolan-4-yl) methyl (meth) acrylate), (2- methyl -2- ethyl -1,3- dioxy ring is amyl- 4- yl) methyl (methyl) acrylate ((2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) Acrylate), (Isosorbide-5-Nitrae-dioxy loop coil [4,5] decyl- 2- yl) methyl (methyl) acrylate ((Isosorbide-5-Nitrae-dioxaspiro [4,5] Dec-2-yl) methyl (meth) acrylate), (2, the 2- amyl- 4- yl of dimethyl -1,3- dioxy ring) methyl (methyl) acrylic acid The five-membered ring class of ester ((2,2-dimethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate) etc.；(methyl) third Dimethomorph ((meth) acryloyl morpholine), (methyl) acrylic acid tetrahydropyrans ester, (methyl) acrylic acid -2- first The six membered ring class of base tetrahydropyrans ester etc..Wherein, cyclic ether group acrylate more than four membered ring or four membered ring of preferably having is Monomer, the cyclic ether group acrylate more preferably having more than five-membered ring or five-membered ring is monomer.
Monomer (a-1-2) individually a kind of can use or mix a variety of uses.
Total amount based on monomer mixture is 100 parts by weight, and the usage amount of monomer (a-1-2) is 3 parts by weight to 20 weight Part, preferably 5 parts by weight to 20 parts by weight, more preferably 5 parts by weight to 15 parts by weight.
As unused monomer (a-1-2), the sensitivity of chemical amplification positive photosensitive resin composition is bad and institute's shape At photoresist pattern rectangularity it is poor.
In the first mixture of the invention, as long as not influencing effect of the invention, other monomers (a- can further include 1-3).Other monomers (a-1-3) are, for example, known free-radical polymerised compound or anionic polymerisation compound.
As such polymerizable compound, the monocarboxylic acid class such as acrylic acid, methacrylic acid, crotonic acid can be enumerated；Horse Carry out the omega-dicarboxylic acids such as sour, fumaric acid, itaconic acid；2- methylacryoyloxyethyl succinic acid, 2- methylacryoyloxyethyl Malaysia Acid, 2- methylacryoyloxyethyl phthalic acid, 2- methylacryoyloxyethyl hexahydrophthalic acid etc. have carboxyl and ester The methacrylic acid derivative class of key；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (first Base) (methyl) alkyl-acrylates such as cyclohexyl acrylate, (methyl) acrylic acid third butyl ester；1- ethyoxyl (methyl) propylene (methyl) alkoxyalkyl acrylates such as acetoacetic ester, 1- methoxyl group (methyl) propyl acrylate；2- adamantyl (methyl) third Olefin(e) acid ester (2-adamantyl (meth) acrylate), 2- methyl -2- adamantyl (methyl) acrylate (2-methyl-2- Adamantyl (meth) acrylate), 2- ethyl -2- adamantyl (methyl) acrylate (2-ethyl-2-adamantyl (meth) acrylate), 2- butyl -2- adamantyl (methyl) acrylate (2-butyl-2-adamantyl (meth) Acrylate), 2- acrylic acid-2- methyl-1-methyl-1-tricyclic [3,3,1,13.7] decyl- 2- base ethyl ester (2-propenoic Acid, 2-methyl-, l-methyl-1-tricyclo [3.3.1.13 ' 7] dec-2-ylethyl ester) etc. contain adamantane (methyl) acrylate of base；(methyl) third such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate Olefin(e) acid hydroxy alkyl esters；(methyl) Glycidyl Acrylate, (methyl) acrylic acid -2- methyl polyglycidyl, (methyl) propylene Acid -3,4- epoxy butyl ester, (methyl) acrylic acid -6,7- epoxy heptyl ester, (methyl) acrylic acid -3,4- epoxy cyclohexyl or (methyl) Acrylic acid -3,4- epoxycyclohexanecarboxylate etc. (methyl) acrylic acid epoxy base ester class；(methyl) phenyl acrylate, (methyl) propylene Sour benzene methyl etc. (methyl) benzyl acrylate class；The dicarboxylic diesters class such as diethyl maleate, dibutyl fumarate；Benzene second Alkene, α-methylstyrene, chlorostyrene, 1-chloro-4-methyl-benzene, vinyltoluene, hydroxy styrenes, Alpha-Methyl hydroxy styrenes, The aromatic compound species containing vinyl such as α-ethyl hydroxy styrene；The aliphatic compound containing vinyl such as vinyl acetate Class；Butadiene, isoprene equiconjugate alkadiene；The polymerizable compound class of the nitrile group-containings such as acrylonitrile, methacrylonitrile；Chlorine The polymerizable compounds containing chlorine such as ethylene, vinylidene chloride；The polymerism chemical combination of the amide bonds such as acrylamide, Methacrylamide Species etc..
Total usage amount based on the first mixture is 100 parts by weight, the contents of other monomers (a-1-3) be 30 parts by weight extremely To 85 parts by weight, more preferably 45 parts by weight to 85 parts by weight are more preferably for 87 parts by weight, preferably 35 parts by weight.
The weight average molecular weight of resin (A-1) is 5,000 to 30,000；Preferably 6,000 to 25,000；More preferably 7, 000 to 20,000.
Resin (A-2)
Resin (A-2) of the invention is to be reacted by the second mixture and obtained, which includes monomer (a-2-1), Or it can further include monomer (a-2-2).
Monomer (a-2-1) of the invention stretches alkyl chain containing polyoxy, can enumerate following concrete examples, but be not restricted to this A little concrete examples: acrylic acid phenyl methylcarbamate ester (trade name: ARONIX TO-901), the E0 of ethylene oxide (hereinafter referred to as EO) modification change The acrylic acid tridecane ester (trade name: ARONIX that lauryl ester (trade name: ARONIX T0-950), the E0 of matter are modified TO-951), acrylic acid (2- ethylhexyl-polyethylene glycol) ester (trade name: ARONIX TO-946~TO-949), the above are east Manufactured by the synthesis limited liability company of Asia；Acrylic acid (ethyl-diethylene glycol) ester (trade name: Light Acrylate EC-A), Acrylic acid (methoxy-triethylene glycol) ester (trade name: Light Acrylate MTG-A), acrylic acid (the poly- second two of methoxyl group- Alcohol) ester (trade name: Light Acrylate 130A), acrylic acid (phenoxy group-polyethylene glycol) ester (trade name: Light Acrylate P-200A), acrylic acid (nonyl phenyl-polyoxyethanyl chain additives) ester (trade name: Light Acrylate NP-4EA, NP-8EA), the above are manufactured by chemistry limited liability company, common prosperity society；Polyalkylene glycol acrylate ester (trade name: BLEMMER AE-350), methacrylic acid macrogol ester (trade name: BLEMMER PE-90, PE-200, PE-350), propylene Sour (methoxypolyethylene glycol) ester (trade name: BLEMMER AME-400), methacrylic acid (methoxypolyethylene glycol) ester (trade name: BLEMMER PME-100, PME-200, PME-400), methacrylic acid polypropylene glycol ester (trade name: BLEMMER PP-500, PP-800), methacrylic acid (polyethylene glycol propylene glycol) ester (trade name: BLEMMER 70PEP-370B), first (octyloxy-is poly- for base acrylic acid (polyethylene glycol butanediol) ester (trade name: BLEMMER 50PET-800), methacrylic acid Ethylene glycol-polypropylene glycol) ester (trade name: BLEMMER 50POEP-800B, 50AOEP-800B), the above are Japanese grease shares Manufactured by Co., Ltd；Methacrylic acid (methoxyl group-diethylene glycol) ester (trade name: NK Ester M-20G, M-40G, M- 90G) and acrylic acid (phenoxy group-diethylene glycol) ester (trade name: NK Ester AMP-20G), the above are the village Xin Zhong chemistry Manufactured by Industries, Inc.
Total amount based on the second mixture is 100 parts by weight, and the usage amount of monomer (a-2-1) is 5 parts by weight to 50 weight Part, preferably 5 parts by weight to 40 parts by weight, more preferably 10 parts by weight to 40 parts by weight.
As unused monomer (a-2-1), the sensitivity of chemical amplification positive photosensitive resin composition is bad and institute's shape At photoresist pattern rectangularity it is poor.
Monomer (a-2-2) of the invention contains the structure such as formula (a-2-2a):
In formula (a-2-2a), R1bIt is respectively independent to indicate hydrogen atom ,-CH3、-CF3Or-CH20H。R2bIndicate alkyl (carbon number It is preferable for 1 to 8 person), naphthenic base (carbon number is that 3 to 8 persons are preferable) or aryl (carbon number is that 6 to 20 persons are preferable).R3bTo R12bRespectively solely The vertical alkyl (carbon number is that 1 to 15 person is preferable) or R for indicating hydrogen atom or containing or do not contain heteroatomic 1 valence3bTo R12bIn The two more than form ring mutually.When forming ring mutually, R3bTo R12bExpression contains or does not contain heteroatomic divalent alkyl (carbon Number is that 1 to 15 person is preferable).R3bTo R12bExpression is bonded to adjacent carbon person can not be bonded each other between any object, can also be formed Double bond.T indicates the linker of singly-bound or divalent.The divalent linker of T is to stretch alkyl (carbon number is that 1 to 10 person is preferably more preferably carbon Number be 1 to 5) ,-COO-RtBase, -0-RtBase, and RtFor stretch alkyl (carbon number be 1 to 10 person be preferably, more preferably carbon number be 1 to 5) or ring stretches alkyl (carbon number is that 3 to 10 persons are preferable).
R2bIndicate alkyl, naphthenic base or aryl.R2bAlkyl and naphthenic base may be, for example, methyl, ethyl, propyl, isopropyl Base, n- butyl, the second butyl, third butyl, third amyl, n- amyl, n- hexyl, cyclopenta, cyclohexyl, cyclopentyl-methyl, Cyclopentyl ethyl, cyclohexyl methyl, cyclohexyl-ethyl etc..The aryl may be, for example, phenyl, aminomethyl phenyl, naphthalene, anthryl, phenanthrene Base, pyrenyl etc..
R3bTo R12bRespectively it is independent indicate hydrogen atom or contain or not the alkyl containing heteroatomic 1 valence (carbon number be 1 to 15 is preferable) when, it may be, for example, methyl, ethyl, propyl, isopropyl, n- butyl, the second butyl, third butyl, the three penta Base, n- amyl, n- hexyl, n- octyl, n- nonyl, n- decyl, cyclopenta, cyclohexyl, cyclopentyl-methyl, cyclopentyl ethyl, ring The alkyl and naphthenic base of amyl butyl, cyclohexyl methyl, cyclohexyl-ethyl, cyclohexylbutyl etc., and a part of above-mentioned group Hydrogen atom can be by hydroxyl, alkoxy, carboxylic acid group, alkoxy carbonyl group, side oxygen (oxo) base, amido, alkylamino radical, itrile group, mercapto, alkane The groups such as sulfenyl, sulfo group replace.
R3bTo R12bCan also be formed mutually ring (such as: R3bAnd R4b、R5bAnd R7b、R5bAnd R8b、R6bAnd R8b、R6bAnd R12b、R7b And R11b、R9bAnd R10b、R10bAnd R11bDeng), at this point, R3bTo R12bExpression contains or containing heteroatomic divalent alkyl, (carbon number is not 1 to 15 person is preferable), it may be, for example, 1 hydrogen atoms of removal from the example of the alkyl of above-mentioned 1 valence.Furthermore R3bTo R12bTable Show that being bonded to adjacent carbon person can not be bonded each other between any object, double bond (such as R can also be formed3bAnd R12b、R9bAnd R12b、 R5bAnd R7bDeng).
The specific example such as following formula (a-2-2-1) of monomer (a-2-2) is to shown in formula (a-2-2-26).It illustrates, Known method that can be for example contained using Japanese publication number 2000-336121 a case, synthesis following formula (a-2-2-1) to formula (a-2- Compound 2-26).
In the concrete example of above formula (a-2-2a), and by R5bAnd R7bBond and formed with following formula (a-2-2b) The norbornane ring of structure is preferable.
In formula (a-2-2b), R1bIt is respectively independent to indicate hydrogen atom ,-CH3、-CF3Or-CH2OH。R2bIndicate alkyl (carbon number It is preferable for 1 to 8 person), naphthenic base (carbon number is that 3 to 8 persons are preferable) or aryl (carbon number is that 6 to 20 persons are preferable).R3b、R4b、R6b、R8b To R18bThe respectively independent alkyl (carbon number is that 1 to 15 person is preferable) for indicating hydrogen atom or containing or do not contain heteroatomic 1 valence, Or R3b、R4b、R6b、R8bTo R18bBoth of above form ring mutually.When forming ring mutually, R3b、R4b、R6b、R8bTo R18bTable Show containing or do not contain heteroatomic divalent alkyl (carbon number is that 1 to 15 person is preferable).R3b、R4b、R6b、R8bTo R18bExpression is bonded to Adjacent carbon person can not be bonded each other between any object, can also form double bond.T indicates the linker of singly-bound or divalent.The divalent of T Linker is to stretch alkyl (carbon number is that 1 to 10 person is that preferably, more preferably carbon number is 1 to 5) ,-COO-RtBase, -0-RtBase, and Rt For stretch alkyl (carbon number is that 1 to 10 person is preferably, and more preferably carbon number be 1 to 5) or ring stretch alkyl (carbon number be 3 to 10 persons for compared with It is good).
Total amount based on the second mixture is 100 parts by weight, and the usage amount of monomer (a-2-2) is 3 parts by weight to 20 weight Part, preferably 3 parts by weight to 15 parts by weight, more preferably 5 parts by weight to 15 parts by weight.
When the second mixture contains monomer (a-2-2), formed by chemical amplification positive photosensitive resin composition Photoresist pattern rectangularity it is preferable.
In the second mixture of the invention, as long as not influencing effect of the invention, other monomers (a- can further include 2-3).Other monomers (a-2-3) are, for example, known free-radical polymerised compound or anionic polymerisation compound.
As such polymerizable compound, the monocarboxylic acid class such as acrylic acid, methacrylic acid, crotonic acid can be enumerated；Horse Carry out the omega-dicarboxylic acids such as sour, fumaric acid, itaconic acid；2- methylacryoyloxyethyl succinic acid, 2- methylacryoyloxyethyl Malaysia Acid, 2- methylacryoyloxyethyl phthalic acid, 2- methylacryoyloxyethyl hexahydrophthalic acid etc. have carboxyl and ester The methacrylic acid derivative class of key；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (first Base) (methyl) alkyl-acrylates such as cyclohexyl acrylate, (methyl) acrylic acid third butyl ester；1- ethyoxyl (methyl) propylene (methyl) alkoxyalkyl acrylates such as acetoacetic ester, 1- methoxyl group (methyl) propyl acrylate；2- adamantyl (methyl) third Olefin(e) acid ester (2-adamantyl (meth) acrylate), 2- methyl -2- adamantyl (methyl) acrylate (2-methyl-2- Adamantyl (meth) acrylate), 2- ethyl -2- adamantyl (methyl) acrylate (2-ethyl-2-adamantyl (meth) acrylate), 2- butyl -2- adamantyl (methyl) acrylate (2-butyl-2-adamantyl (meth) Acrylate), 2- acrylic acid-2- methyl-1-methyl-1-tricyclic [3,3,1,13.7] decyl- 2- base ethyl ester (2-propenoic Acid, 2-methyl-, 1-methyl-1-tricyclo [3.3.1.13,7] dec-2-ylethyl ester) etc. contain adamantane (methyl) esters of acrylic acid of base；(methyl) such as (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylates Hydroxyalkyl acrylates class；(methyl) Glycidyl Acrylate, (methyl) acrylic acid -2- methyl polyglycidyl, (methyl) third Olefin(e) acid -3,4- epoxy butyl ester, (methyl) acrylic acid -6,7- epoxy heptyl ester, (methyl) acrylic acid -3,4- epoxy cyclohexyl or (first Base) the acrylic acid epoxies base ester class such as acrylic acid -3,4- epoxycyclohexanecarboxylate；(methyl) phenyl acrylate, (methyl) acrylic acid Benzene methyl etc. (methyl) benzyl acrylate class；The dicarboxylic diesters class such as diethyl maleate, dibutyl fumarate；Styrene, α-methylstyrene, chlorostyrene, 1-chloro-4-methyl-benzene, vinyltoluene, hydroxy styrenes, Alpha-Methyl hydroxy styrenes, α- The aromatic compound species containing vinyl such as ethyl hydroxy styrene；The aliphatic compound containing vinyl such as vinyl acetate Class；Butadiene, isoprene equiconjugate alkadiene；The polymerizable compound class of the nitrile group-containings such as acrylonitrile, methacrylonitrile；Chlorine The polymerizable compounds containing chlorine such as ethylene, vinylidene chloride；The polymerism chemical combination of the amide bonds such as acrylamide, Methacrylamide Species etc..
Total usage amount based on the second mixture is 100 parts by weight, the contents of other monomers (a-2-3) be 30 parts by weight extremely To 92 parts by weight, more preferably 45 parts by weight to 85 parts by weight are more preferably for 92 parts by weight, preferably 45 parts by weight.
The weight average molecular weight of resin (A-2) is 5,000 to 30,000；Preferably 6,000 to 25,000；More preferably 7, 000 to 20,000.
Total usage amount based on resin (A) is 100 parts by weight, and the content of resin (A-1) is 60 parts by weight to 90 parts by weight, Preferably 60 parts by weight are to 85 parts by weight, more preferably 60 parts by weight to 80 parts by weight；The content of resin (A-2) be 10 parts by weight extremely 40 parts by weight, preferably 15 parts by weight are to 40 parts by weight, more preferably 20 parts by weight to 40 parts by weight.
When resin (A-1) and resin (A-2) content within the above range, by chemical amplification positive photoresist group The rectangularity for being formed by photoresist pattern at object is preferable.
The solvent for preparing resin (A-1) and/or resin (A-2) Shi Suoyong includes but is not limited to (1) alcohol compound: first Alcohol, ethyl alcohol, benzyl alcohol, 2 phenylethyl alcohol or 3- phenyl-1-propanol etc.；(2) ether compound: tetrahydrofuran etc.；(3) glycol ethers Class compound: ethylene glycol ether, glycol monoethyl ether, ethylene glycol monoethyl ether etc.；(4) ethylene glycol alkyl ether acetate: second two Alcohol monobutyl ether acetate, ethylene glycol ether acetate, glycol methyl ether acetate etc.；(5) diethylene glycol class compound: diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether (diethylene glycol Dimethyl ether), diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether etc.；(6) dipropylene glycol class compound: dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether etc.；(7) the third two Alcohol monoalkyl ether compound: propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.；(8) Propylene glycol alkyl ether acetate class compound: propylene glycol methyl ether acetate (propylene glycol monomethyl ether Acetate), propylene-glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate etc.；(9) propylene glycol alkyl ether Propionic acid ester compound: propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propandiol butyl ether Propionic ester etc.；(10) compound fragrant hydrocarbon: toluene, dimethylbenzene etc.；(11) ketone compounds: methyl ethyl ketone, cyclohexanone, diacetone Alcohol etc.；(12) ester type compound: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2- hydroxyl Base -2 Methylpropionic acid methyl esters, 2- hydroxy-2-methyl ethyl propionate, glycolic acid methyl esters, ethyl glycolate, butyl glycolate, lactic acid Methyl esters, propyl lactate, butyl lactate, 3- hydroxy methyl propionate, 3- hydroxypropionate, 3- hydracrylic acid propyl ester, 3- hydroxyl third Acid butyl ester, 2- hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, second Ethoxyacetic acid methyl esters, ethoxy ethyl acetate, ethoxyacetic acid propyl ester, ethoxyacetic acid butyl ester, propoxyl group methyl acetate, the third oxygen Ethyl, propoxyl group propyl acetate, propoxyl group butyl acetate, butoxy acetic acid methyl esters, butoxy acetic acid ethyl ester, butoxy Propyl acetate, butoxy acetic acid butyl ester, 3- methoxybutyl acetic acid esters, 2- methoxy methyl propionate, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- methoxy propyl acid butyl ester, 2- ethoxypropanoate, 2- ethoxyl ethyl propionate, 2- ethyoxyl Propyl propionate, 2- ethoxy-c acid butyl ester, 2- butoxy methyl propionate, 2- butoxy ethyl propionate, 2- butoxy propyl propionate, 2- butoxy butyl propionate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- methoxy propyl propyl propionate, 3- methoxyl group Butyl propionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 3- ethoxy-c propyl propionate, 3- ethoxy-c acid butyl ester, 3- propoxyl group methyl propionate, 3- propoxyl group ethyl propionate, 3- propoxyl group propyl propionate, 3- propoxyl group butyl propionate, 3- butoxy Methyl propionate, 3- butoxy ethyl propionate, 3- butoxy propyl propionate, 3- butoxy butyl propionate etc., this solvent can individually or It is used in mixed way.
Used polymerization initiators are prepared when resin (A-1) and/or resin (A-2) including but not limited to azo-compound Or peroxide, it can be used alone or as a mixture.
Azo-compound is such as, but not limited to: 2,2 '-azobis isobutyronitriles, 2,2 '-azos are bis- (2,4- methyl pentane nitrile) [2,2 '-azobis (2,4-dimethylvaleronitrile)], bis- (4- methoxyl group -2, the 4- dimethyl-pentens of 2,2 '-azos Nitrile), 2,2 '-azos double -2- methylbutyronitriles [2,2 '-azobis-2-methyl butyronitrile], 4, the 4 '-bis- (4- of azo Cyanopentanoic acid), 2,2 '-azo of dimethyl bis- (2 Methylpropionic acid esters), bis- (4- methoxyl group -2, the 4- dimethyl-pentens of 2,2 '-azos Nitrile) etc..
Peroxide is such as, but not limited to: dibenzoyl peroxide, dilauroyl peroxide, third butyl peroxy the three penta Acid esters, 1,1- bis- (third butyl peroxy) hexamethylene, hydrogen peroxide etc..
Reaction temperature when preparing resin (A-1) and/or resin (A-2) is 40~120 degree, and polymerization time is 3~12 small When.
Novolac resin (B)
Novolac resin (B) is passed through in the presence of acidic catalyst by aldehyde compound and aromatic hydroxy compound Polycondensation reaction and obtain.
The concrete example of aforementioned aldehyde compound, such as: formaldehyde, paraformaldehyde (paraformaldehyde), metaformaldehyde (trioxane), acetaldehyde, propionic aldehyde, butyraldehyde, trimethyl-acetaldehyde, methacrylaldehyde (acrolein), crotonaldehyde (crotonaldehyde), Hexamethylene aldehyde (cyclo hexanealdehyde), furtural (furfural), furylacrolein (furylacrolein), Benzaldehyde, terephthalaldehyde (terephthal aldehyde), phenylacetaldehyde, α-hydrocinnamicaldehyde, beta-phenyl propionic aldehyde, ortho-methyl benzene Formaldehyde, m- tolyl aldehyde, p-tolualdehyde, o- chlorobenzaldehyde, m- chlorobenzaldehyde, p- chlorobenzaldehyde, cinnamic acid Deng.Aforementioned aldehyde compound individually a kind of can use or mix a variety of uses.Preferably, aldehyde compound can be formaldehyde or benzene first Aldehyde.
The concrete example of aforementioned fragrance race hydroxy compounds, such as: phenol (phenol)；M-cresol (m-cresol), p- first Phenol (p-cresol), o-cresol (o-cresol) etc. cresols (cresol) class compound；2,3- dimethlbenzenes, 2,5- dimethylbenzene Phenol, 3,5- dimethlbenzene, 3,4- table cresols etc. xylenols (xylenol) class compound；M- ethyl -phenol, p- ethylo benzene Phenol, o- ethyl -phenol, 2,3,5-TEP, 2,3,5- triethyl group phenol, 4- third butylphenol, 3- third butyl benzene Phenol, 2- third butylphenol, 2- third butyl -4- methylphenol, 2- third butyl -5- methylphenol, 6- third butyl -3- first The alkylphenols such as base phenol (alkyl phenol) class compound；P-methoxyphenol, m- metoxyphenol, p- ethyoxyl Phenol, m- thanatol, to propoxyl group phenol, m- propoxyl group phenol etc. alkoxy phenols (alkoxy phenol) class Close object；O- isopropenyl phenol, p- isopropenyl phenol, 2- methyl -4- isopropenyl phenol, 2- ethyl -4- isopropenyl The isopropenyl phenols such as phenol (isopropenyl phenol) class compound；The aryl of phenylphenol (phenyl phenol) Phenol (aryl phenol) class compound；4,4 '-dihydroxybiphenyls, bisphenol-A, m- benzenediol (resorcinol), p- benzene two Phenol (hydroquinone), Pyrogallol acid (pyrogallol) etc. polyhydroxy benzenes (polyhydroxyphenol) class chemical combination Object.Aromatic hydroxy compound individually a kind of can use or mix a variety of uses.
Preferably, aromatic hydroxy compound can be 3,5- dimethlbenzene, 3,4-Xylenol, 2,5- dimethlbenzene, o- Cresols, m-cresol or p-Cresol.
The concrete example of aforementioned acid catalyst, such as: hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or p-methyl benzenesulfonic acid.
Novolac resin (B) individually a kind of can use or mix a variety of uses.Total usage amount based on resin (A) is 100 parts by weight, the content of novolac resin (B) are 20 parts by weight to 180 parts by weight, preferably 25 parts by weight to 160 weight Part, more preferably 30 parts by weight to 140 parts by weight.
The weight average molecular weight of novolac resin (B) is 5,000 to 50,000；Preferably 6,000 to 45,000；More Good is 7,000 to 40,000.
Photoacid generator (C)
Photoacid generator (C) is the irradiation by actinic ray or radioactive ray and generates the compound of acid, as long as that can borrow The compound that acid is directly or indirectly generated by light, is not particularly limited.As photoacid generator (C), preferably following institute First illustrated~the 5th form acid producing agent.Hereinafter, to the photoacid generator used is suitble in photosensitive resin composition (C) preferably in is illustrated in the form of first to the 5th.
As the first form of photoacid generator (C), following formula (C-1) compound represented can be enumerated:
In formula (C-1), X1Indicate that the sulphur atom or iodine atom of g valence, g are 1 or 2.H indicates the repetition list of the structure in parantheses First number.W1For with X1The organic group of bond, indicate carbon number be 6 to 30 aryl, carbon number be 4 to 30 heterocycle, carbon number be 1 to The alkynyl that the alkenyl or carbon number that 30 alkyl, carbon number are 2 to 30 are 2 to 30, W1It can be via alkyl, hydroxyl, alkoxy, alkane carbonyl Base, aromatic carbonyl, alkoxy carbonyl group, aryloxy carbonyl, fragrant thiocarbonyl group, acyloxy, arylthio, alkylthio group, aryl, heterocycle, aryloxy group, alkane Sulfinyl, alkane sulfonyl, arylsulfonyl, stretches alkoxy, amido, cyano, group formed by nitro and halogen at fragrant sulfinyl In at least one kind of substitution for selecting.W1Number be g+h (g-1)+1, W1It can distinguish mutually the same or different.Also, 2 or more W1 It can be bonded directly with one another or via-O- ,-S- ,-SO- ,-S02-、-NH-、-NW2,-CO- ,-COO- ,-CONH-, carbon number be 1 to 3 stretch alkyl or stretch phenyl bond and formed includes X1Ring structure.W2For carbon number be 1 to 5 alkyl or carbon number be 6 to 10 Aryl.
X2For structure shown in following formula (C-1a):
In formula (C-la), X4Indicate carbon number be 1 to 8 stretch alkyl, carbon number be 6 to 20 stretch aryl or carbon number is 8 to 20 The miscellaneous base of divalent, X4Aryl that alkoxy that the alkyl that can be 1 to 8 via carbon number, carbon number are 1 to 8, carbon number are 6 to 10, hydroxyl, At least one kind of substitution selected in group formed by cyano, nitro and halogen.X5Expression-O- ,-S- ,-SO- ,-SO2-、-NH-、- NW2,-CO- ,-COO- ,-CONH-, carbon number be 1 to 3 to stretch alkyl or stretch phenyl.H indicates the repetitive unit of the structure in parantheses Number.H+1 X4And h X5It can distinguish identical or different.W2It is identical as aforementioned definitions.
(X3)-be to ion (counter ion), can enumerate fluoroalkyl fluorophosphoric acid shown in following formula (C-1b) yin The anion of borate anion, the anion of following formula (C-1d) or following formula (C-1e) shown in ion, following formula (C-1c):
[(W3)jPF6-j]-Formula (C-1b)
In formula (C-1b), W3The alkyl that the hydrogen atom of 80% or more expression replaces through fluorine atom.J indicates its number, be 1 to 5 integer.J W3It can distinguish identical or different.
In formula (C-1c), W4~W7Independently indicate fluorine atom or phenyl, a part of the hydrogen atom in the phenyl or complete It portion can be via at least one kind of substitution selected in group formed by fluorine atom and trifluoromethyl.
R1dS03 -Formula (C-1d)
Anion representated by formula (C-1d) may be, for example, trifluoromethanesulfonic acid anion, five fluorine ethanesulfonic acid anion, seven fluorine Propane sulfonic acid anion, nine fluorine fourth sulfonic acid anions, phenyl-pentafluoride sulfonic acid anion, p- toluenesulfonate anion, benzene sulfonic acid yin from Son, naphthalene sulfonic acids anion, rylnthracene sulfonin anion, camphorsulfonic acid anion, methylsulphur acid anion, ethanesulfonic acid anion, propane sulfonic acid Anion and fourth sulfonic acid anion.Wherein, preferably trifluoromethanesulfonic acid anion, nine fluorine fourth sulfonic acid anions, benzene sulfonic acid yin from Sub or p- toluenesulfonate anion.
(R2bS02)3C-Formula (C-le)
Anion shown in formula (C-1e) may be, for example, (CF3S02)3C-、(C2F5S02)3C-、(C3F7SO2)3C-Or (C4F9S02)3C-。
As the ion in formula (C-1) compound represented, triphenylsulfonium, three-p-methylphenyl sulfoniums, 4- (benzene can be enumerated Sulfenyl) phenyl diphenyl sulfonium, bis- [4- (diphenyl sulfonium base) phenyl] thioethers, bis- [4- { bis- [4- (2- hydroxy ethoxy) phenyl] sulfoniums Base } phenyl] thioether, bis- { 4- [bis- (4- fluorophenyl) sulfonium bases] phenyl } thioethers, 4- (4- benzoyl -2- chlorophenylsulfanyl) phenyl pair (4- fluorophenyl) sulfonium, 7- isopropyl -9- Oxy-1 0- thia -9,10- dihydroanthracene -2- two-p-methylphenyl of base sulfonium, 7- isopropyl - 9- Oxy-1 0- thia -9,10- dihydroanthracene -2- base diphenyl sulfonium, 2- [(diphenyl) sulfonium base] thioxanthone, 4- [4- (4- third Butylbenzoyl) thiophenyl] two-p-methylphenyl of phenyl sulfonium, 4- (4- benzoylphenylsulfanyl) phenyl diphenyl sulfonium, diphenyl Phenylacetyl group sulfonium, 4- hydroxyphenylmethyl benzyl sulfonium, 2- naphthyl methyl (1- carbethoxyl group) ethyl sulfonium, 4- hydroxyphenylmethyl benzene second Acyl group sulfonium, phenyl [4- (4- biphenyl sulfenyl) phenyl] 4- biphenyl sulfonium, phenyl [4- (4- biphenyl sulfenyl) phenyl] 3- biphenyl sulfonium, [4- (4- acetyl thiophenyl) phenyl] diphenyl sulfonium, octadecyl methyl phenylacetyl group sulfonium, two benzene base Iodonium, two-to first benzene base Iodonium, bis- (4- Dodecyl phenyl) Iodonium, bis- (4- methoxyphenyls) lock, (4- octyloxyphenyl) benzene base Iodonium, bis- (12 oxygroup of 4-) benzene base Iodonium, 4- (14 oxygroup of 2- hydroxyl) phenyl Ben Ji Iodonium, 4- cumenyl (p-methylphenyl) Iodonium, 4- isobutylphenyl (p-methylphenyl) Iodonium or double (4- third butyl phenyl) iodine etc..
In ion in above-mentioned formula (C-1) compound represented, following formula (C- can be enumerated as preferable ion Sulfonium cation shown in 1f):
In formula (C-1f), W8It independently indicates by hydrogen atom, alkyl, hydroxyl, alkoxy, alkyl carbonyl, alkane carbonyloxy group, alkane Oxygen carbonyl, halogen atom, the aryl that can have substituent group, the base selected in group formed by aromatic carbonyl.X2It indicates and above-mentioned formula (C-1) In X2Identical meaning.
As the specific example of sulfonium cation shown in above-mentioned formula (C-1f), can enumerate 4- (thiophenyl) phenyl diphenyl sulfonium, Bis- (4- fluorophenyl) sulfoniums of 4- (4- benzoyl -2- chlorophenylsulfanyl) phenyl, 4- (4- benzoylphenylsulfanyl) phenyl diphenyl sulfonium, Phenyl [4- (4- biphenyl sulfenyl) phenyl] 4- biphenyl sulfonium, phenyl [4- (4- biphenyl sulfenyl) phenyl] 3- biphenyl sulfonium, [4- (4- acetyl Thiophenyl) phenyl] diphenyl sulfonium, diphenyl [4- (to three thiophenyls) phenyl] diphenyl sulfonium.
In fluoroalkyl fluorophosphoric acid anion shown in above-mentioned formula (C-1b), W3Indicate the alkyl replaced through fluorine atom, preferably Carbon number be 1~8, more preferably carbon number be 1~4.As the specific example of alkyl, methyl, ethyl, propyl, butyl, penta can be enumerated The straight chained alkyls such as base, octyl；The branched alkyl groups such as isopropyl, isobutyl group, the second butyl, third butyl；Even cyclopropyl, ring fourth Naphthenic base such as base, cyclopenta, cyclohexyl etc., it is usually 80% or more that the hydrogen atom of alkyl, which is substituted as the ratio of fluorine atom, compared with Good is 90% or more, more preferably 100%.If the Replacement rate of fluorine atom is not up to 80%, fluoroalkyl shown in above-mentioned formula (C-1) The acid strength of fluorophosphate can reduce.
Particularly good W3It is 1~4 for carbon number, and the Replacement rate of fluorine atom is 100% straight-chain or the perfluor alkane of branch-like Base can enumerate CF as specific example3、CF3CF2、(CF3)2CF、CF3CF2CF2、CF3CF2CF2CF2、(CF3)2CFCF2、CF3CF2 (CF3)CF、(CF3)3C。W3Number j be 1~5 integer, preferably 2~4, particularly good is 2 or 3.
As the specific example of preferable fluoroalkyl fluorophosphoric acid anion, [(CF can be enumerated3CF2)2PF4]-、[(CF3CF2)3PF3]-、[((CF3)2CF)2PF4]-、[((CF3)2CF)3PF3]-、[(CF3CF2CF2)2PF4]-、[(CF3CF2CF2)3PF3]-、 [((CF3)2CFCF2)2PF4]-、[((CF3)2CFCF2)3PF3]-、[(CF3CF2CF2CF2)2PF4]-or [(CF3CF2CF2)3PF3]-, In these, particularly good is [(CF3CF2)3PF3]-、[(CF3CF2CF2)3PF3]-、[((CF3)2CF)3PF3]-、[((CF3)2CF)2PF4]-、[((CF3)2CFCF2)3PF3]-Or [((CF3)2CFCF2)2PF4]-。
As the preferred embodiments of borate anion shown in above-mentioned formula (C-1c), wantonly (pentafluorophenyl group) boron can be enumerated Acid group ([B (C6F5)4]-), wantonly [(trifluoromethyl) phenyl] borate ([B (C6H4CF3)4]-), bis- (pentafluorophenyl group) boric acid of difluoro Root ([(C6F5)2BF2]-), trifluoro (pentafluorophenyl group) borate ([(C6F5)BF3]-), wantonly (difluorophenyl) borate ([B (C6H3F2)4]-) etc..It is particularly good for wantonly (pentafluorophenyl group) borate ([B (C in these6F5)4]-)。
As the second form of acid producing agent (A), can enumerate bis- (the trichloromethyl) -6- piperonyl -1,3,5-triazines of 2,4-, 2,4- bis- (trichloromethyl) -6- [2- (2- furyl) vinyl] symmetrical triazine, bis- (trichloromethyl) -6- [2- (the 5- first of 2,4- Base -2- furyl) vinyl] symmetrically triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (5- ethyl -2- furyl) vinyl] are right Claim triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (5- propyl -2- furyl) vinyl] symmetrical triazine, bis- (three chloromethanes of 2,4- Base) -6- [2- (3,5- Dimethoxyphenyl) vinyl] symmetrical triazine, bis- (trichloromethyl) -6- [2- (3, the 5- diethoxies of 2,4- Base phenyl) vinyl] symmetrical triazine, bis- (the trichloromethyl) -6- of 2,4- [2- (3,5- dipropoxy phenyl) vinyl] symmetrical three Bis- (the trichloromethyl) -6- of piperazine, 2,4- [2- (3- methoxyl group -5- ethoxyl phenenyl) vinyl] symmetrical triazine, bis- (three chloromethanes of 2,4- Base) the symmetrical triazine of -6- [2- (3- methoxyl group -5- propoxyphenyl) vinyl], [(3, the 4- Asias 2- bis- (the trichloromethyl) -6- of 2,4- Methylenedioxy group phenyl) vinyl] symmetrical triazine, bis- (the trichloromethyl) -6- (3,4- methylenedioxyphenyl) of 2,4- symmetrically triazine, 2,4- bis--trichloromethyl -6- (the bromo- 4- methoxyl group of 3-) symmetrical triazine of phenyl, 2,4- be bis--trichloromethyl -6- (the bromo- 4- methoxy of 2- Base) the symmetrical triazine of phenyl, 2,4- be bis--and trichloromethyl -6- (the bromo- 4- methoxyl group of 2-) symmetrical triazine of styryl phenyl, 2,4- be bis- - Trichloromethyl -6- (the bromo- 4- methoxyl group of 3-) symmetrical triazine of styryl phenyl, bis- (three chloromethanes of 2- (4- methoxyphenyl) -4,6- Base) -1,3,5-triazines, bis- (the trichloromethyl) -1,3,5-triazines of 2- (4- methoxyl group naphthalene) -4,6-, 2- [2- (2- furyl) second Alkenyl] bis- (the trichloromethyl) -1,3,5-triazines of -4,6-, 2- [2- (5- methyl -2- furyl) vinyl] bis- (three chloromethanes of -4,6- Base) -1,3,5-triazines, 2- [2- (3,5- Dimethoxyphenyl) vinyl] bis- (trichloromethyl) -1,3,5-triazines of -4,6-, 2- [2- (3,4- Dimethoxyphenyl) vinyl] bis- (trichloromethyl) -1,3,5-triazines of -4,6-, 2- (3,4- methylenedioxybenzenes Base) bis- (the trichloromethyl) -1,3,5-triazines of -4,6-, ginseng (1,3- dibromopropyl) -1,3,5-triazines, ginseng (2,3- dibromopropyl) - The following formula (C-2) such as the halogen-containing triaizine compounds such as 1,3,5-triazines and ginseng (2,3- dibromopropyl) isocyanuric acid ester Shown in halogen-containing triaizine compounds.
In formula (C-2), W9~W11Independently it is expressed as alkylhalide group.
Also, the third form as photoacid generator (C), can enumerate α-(tolysulfonyl oxygroup imido grpup)-phenyl second Nitrile, α-(phenylsulfonyloxy imido grpup) -2,4- dichlorophenyl acetonitrile, α-(phenylsulfonyloxy imido grpup) -2,6- dichlorophenyl second Nitrile, α-(2- chloro benzenesulfonyloxy imido grpup) -4- methoxyphenylacetonitrile, α-(ethylsulfonyloxy imido grpup) -1- chlorine amylene Base acetonitrile and following formula (C-3) compound represented containing sulfonic acid oximido.
In formula (C-3), W12Indicate 1 valence, divalent or trivalent organic group, W13Expression is substituted or unsubstituted saturated hydrocarbons Base, unsaturated alkyl or aromatic series compound base, n indicate the number of repeat unit of the structure in parantheses.
In above-mentioned formula (C-3), aromatic series compound basis representation makes aromatic compound show distinctive physics, chemically The base of the compound of matter can enumerate the heteroaryls such as the aryl such as phenyl, naphthalene or furyl, thienyl.These also can be in ring Above with 1 or more substituent group appropriate, such as halogen atom, alkyl, alkoxy, nitro etc..Also, W13It is particularly good to be for carbon number 1 to 6 alkyl can enumerate methyl, ethyl, propyl, butyl.Especially with W12For aromatic series compound base, W13It is 1 to 4 for carbon number The compound of alkyl be preferable.
As acid producing agent shown in above-mentioned formula (C-3), as n=1, W can be enumerated12For phenyl, aminomethyl phenyl, methoxyl group Phenyl is any, W13For the compound of methyl, α-(mesyloxy imido grpup) -1- phenylacetonitrile, α-can be specifically enumerated (mesyloxy imido grpup) -1- (p-methylphenyl) acetonitrile, α-(mesyloxy imido grpup) -1- (p- methoxyphenyl) second Nitrile, [2- (the third sulfonyloxy imido grpup) -2,3- dihydroxy thiophene -3- subunit] (o-tolyl) acetonitrile etc..As n=2, as Acid producing agent shown in above-mentioned formula (C-3) can specifically enumerate the generation of acid shown in following formula (C-3-1)~formula (C-3-8) Agent:
In addition, the 4th form as photoacid generator (C), can enumerate the salt that cationic portion has naphthalene nucleus.It should " tool Have naphthalene nucleus " refer to structure derived from naphthalene, it is intended that the structure of at least two ring, and the meaning of the armaticity of they can be maintained.It should Naphthalene nucleus can also have the straight-chain or branch that alkyl, hydroxy, the carbon number of the straight-chain or branch-like that carbon number is 1 to 6 are 1 to 6 The substituent group of the alkoxy of shape etc..Structure derived from naphthalene nucleus can be 1 valence base (free valence is 1), also can be (the trip of divalent base From valence be 2) more than, it is more satisfactory be 1 valence base (only, at this point, be deduct with above-mentioned substituent group bond close part come calculate trip From valence).Naphthalene nucleus number is preferably 1~3.
There is the cationic portion of the salt of naphthalene nucleus as such cationic portion, preferably shown in following formula (C-4) Structure:
In formula (C-4), W14~W16In at least 1 indicate following formula (C-4a) shown in base, remaining indicate carbon number be 1 to 6 Straight-chain or the alkyl of branch-like, the phenyl that can have substituent group, hydroxy or carbon number be 1 to 6 straight-chain or branch The alkoxy of shape.Alternatively, W14~W16One of for base shown in following formula (C-4a), both remaining is each independently carbon number 1 Straight-chain or branch-like to 6 stretch alkyl, these end can be bonded and annular in shape.
In formula (C-4a), W17、W18Independently indicate the alkane of hydroxy, the straight-chain that carbon number is 1 to 6 or branch-like The alkyl of straight-chain or branch-like that oxygroup or carbon number are 1 to 6, W18It indicates singly-bound or can have the carbon number of substituent group to be 1 to 6 Straight-chain or branch-like stretch alkyl.1 and m independently indicates that 0~2 integer, l+m are 3 or less.Work as W17There are multiple When, they can be mutually the same or different.Work as W18There are it is multiple when, they can be mutually the same or different.
Above-mentioned W14~W16The number of base shown in above-mentioned formula (C-4a), the stability viewpoint based on compound are preferable in the middle It is 1, remaining is that the straight-chain that carbon number is 1 to 6 or branch-like stretch alkyl, these end can be bonded and annular in shape.At this point, Stretching alkyl for above-mentioned 2 may include sulphur atom and constitutes 3 to 9 Yuans rings.Constitute ring atom (sulfur atom-containing) number be preferably 5 to 6。
Also, oxygen atom can be enumerated (at this point, with the carbon original for stretching alkyl is constituted as the above-mentioned substituent group stretching alkyl and can having Carbonyl is collectively formed in son), hydroxy etc..
Also, hydroxy can be enumerated as the substituent group that phenyl can have, the alkane of the straight-chain that carbon number is 1 to 6 or branch-like Oxygroup, the straight-chain that carbon number is 1 to 6 or alkyl of branch-like etc..
Category is suitable as these cationic portions person, following formula (C-4b), (C-4c) those shown can be enumerated, especially with following formula (C-4c) structure shown in is preferred.
As such cationic portion, Ke Wei Iodonium salt or sulfonium salt；More satisfactory based on viewpoints such as sour generation efficiencies is sulfonium salt.
To more satisfactory for can shape for being suitable as the anion part person of salt of the cationic portion with naphthalene nucleus At the anion of sulfonium salt.
It is part or all of perfluorinated fluoroalkyl sulfonic acids of hydrogen atom as the anion part of such acid producing agent Ion or aryl sulfonic acid ion.
Alkyl in fluoroalkyl sulfonic acids ion can be straight-chain, branch-like or the ring-type that carbon number is 1 to 20, based on generation The volume size and its diffusion length of acid, preferably carbon number are 1 to 10.Especially in branch-like or ring-type person due to diffusion length is short Preferably.Also, methyl, ethyl, propyl, butyl, octyl etc. can be enumerated as preferably for by can inexpensively synthesize.
Aryl in aryl sulfonic acid ion is the aryl that carbon number is 6 to 20, and can enumerate can replace through alkyl, halogen atom Phenyl, naphthalene.In particular, for by can inexpensively synthesize, preferably carbon number be 6 to 10 aryl.As the specific of preferably Example can enumerate phenyl, tosyl, ethylphenyl, naphthalene, methyl naphthalene etc..
Fluorination in above-mentioned fluoroalkyl sulfonic acids ion or aryl sulfonic acid ion, when part or all of hydrogen atom is perfluorinated Rate is preferably 10~100%, more preferably 50~100%, especially the winner with fluorine atom substitution whole hydrogen atoms, because of the intensity of acid Enhancing and it is preferable.Belong to such person, can specifically enumerate triflate, perfluor butanesulfonate, perfluorooctane sulfonate ester, perfluor Benzene sulfonate etc..
In these, as preferable anion part, following formula (C-4d) those shown can be enumerated:
W20S03 -Formula (C-4d)
In formula (C-4d), W20For base shown in following formula (C-4e), (C-4f) and (C-4g).
-CxF2x+1Formula (C-4e)
In formula (C-4e), x indicates 1 to 4 integer.In formula (C-4f), W21Indicate hydrogen atom, hydroxy, carbon atom be 1 to The alkoxy of straight-chain or branch-like that 6 straight-chain or the alkyl of branch-like or carbon number are 1 to 6, y indicate 1 to 3 Integer.In these, triflate, perfluor butanesulfonate are preferably based on safety point.
Also, nitrogenous person shown in following formula (C-4h), formula (C-4i) also can be used as anion part.
In formula (C-4h), formula (C-4i), XaIndicate the straight-chain that replaces through fluorine atom of at least one hydrogen atom or branch-like Alkyl is stretched, which is 2 to 6, preferably 3 to 5, more preferably 3.Also, Ya、ZaIndependently indicate that at least one hydrogen is former The alkyl of straight-chain or branch-like that son replaces through fluorine atom, the carbon number of the alkyl be 1 to 10, preferably 1 to 7, more preferably 1 to 3。
XaThe carbon number or Y for stretching alkyla、ZaAlkyl carbon number it is smaller then better to the dissolubility of organic solvent, because This is preferably.
Also, XaStretch alkyl or Ya、ZaAlkyl in, through fluorine atom replace hydrogen atom number the more, sour intensity is cured By force, therefore preferably.This stretches the ratio of the fluorine atom in alkyl or alkyl, that is, fluorination rate is preferably 70~100%, more preferably 90 ~100%, the perfluor that most preferably all hydrogen atoms replace through fluorine atom stretches alkyl or perfluoroalkyl.
Belong to and be suitable as the salt person that such cationic portion has naphthalene nucleus, following formula (C-4j), formula (C-4k) can be enumerated Compound represented.
Furthermore as the 5th form of photoacid generator (C), can enumerate bis- (p-toluenesulfonyl) diazomethanes, it is bis- (1, 1- dimethylethylsulfonyl) diazomethane, bis- (cyclohexylsulfonyl) diazomethanes, bis- (2,4- 3,5-dimethylphenyl sulfonyls) Double sulfonyidiazomethanes classes such as diazomethane；P-methyl benzenesulfonic acid 2- nitrobenzene methyl esters, p-methyl benzenesulfonic acid 2,6- dinitrobenzene first Ester, toluenesulfonic acid nitrobenzene methyl esters, toluenesulfonic acid dinitrobenzene methyl esters, sulfonic acid nitrobenzene methyl esters, nitrophenylcarbonates methyl esters, carbonic acid The nitrobenzoyls radical derivative such as dinitrobenzene methyl esters；Pyrogallol triflate, pyrogallol front three benzene sulfonate, toluene Sulfonic acid benzene methyl, sulfonic acid benzene methyl, N- mesyloxy succinimide, N- trichloromethyl sulfonyloxy succinimide, N- The sulfonic acid esters such as phenylsulfonyloxy group maleimide, N- mesyloxy phthalimide；N- hydroxyl phthalyl The trifluoromethanesulfonic acids esters such as imines, N- hydroxynaphthylimide；Er Ben Ji Iodonium hexafluorophosphate, (4- methoxyphenyl) Ben Ji Iodonium tri- It is fluorine mesylate, bis- (to third butyl phenyl) Iodonium fluoroform sulphonate, triphenylsulfonium hexafluorophosphate, (4- methoxyphenyl) The salts such as diphenyl sulfonium fluoroform sulphonate, (to third butyl phenyl) diphenyl sulfonium fluoroform sulphonate；Styrax toluene The styraxes toluenesulfonic acid esters such as sulphonic acid ester, Alpha-Methyl styrax tosylate；Other Er Ben Ji Iodonium salt, triphenylsulfonium Salt, Arenediazonium salts, methyl phenyl carbonate etc..
Photoacid generator (C) can be used alone, and can also combine two or more use.Also, being based on total usage amount of resin (A) For 100 parts by weight, the content of photoacid generator (C) is 0.5 parts by weight to 4.5 parts by weight, preferably 0.6 parts by weight to 4 weight Part, more preferably 0.7 parts by weight to 3.5 parts by weight.
Solvent (D)
The type of solvent (D), is not particularly limited in the range of not interfering the object of the invention, can be by being used in eurymeric in the past It is suitable for selecting and using in the organic solvent of photosensitive resin composition.
As the specific example of solvent (D), acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2- heptan can be enumerated The ketones such as ketone；Ethylene glycol, ethylene glycol acetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol list acetic acid The polyalcohols such as ester, dipropylene glycol, the monomethyl ether of dipropylene glycol monoacetate, single ether, single propyl ether, monobutyl ether, monophenyl ether and Its derivative；Two ethers such as glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether；The cyclic ethers class such as dioxanes；First Acetoacetic ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, Ethyl acetoacetate, ethyl pyruvate, ethoxy ethyl acetate, methoxy methyl propionate, 3- ethoxyl ethyl propionate, 2- hydroxyl Methyl propionate, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyl ethyl propionate, 2- hydroxy-3-methyl methyl butyrate, 3- methoxyl group The esters such as butylacetic acid ester, 3- methyl -3- methoxybutyl acetic acid esters, propylene glycol methyl ether acetate；The fragrance such as toluene, dimethylbenzene Race's hydro carbons；Deng.These can be used alone, and can also mix two or more use.
Total usage amount based on resin (A) is 100 parts by weight, and the content of solvent (D) is 60 parts by weight to 800 parts by weight, Preferably 70 parts by weight are to 500 parts by weight, more preferably 80 parts by weight to 400 parts by weight.
Mercaptan compound (E)
Mercaptan compound (E) has structure shown in following formula (E-1):
In formula (E-1), R1c、R2cThe respectively independent alkyl for indicating that hydrogen atom or carbon number are 1 to 4, R3cIndicate singly-bound or carbon number For 1 to 10 alkyl of stretching, R4cIndicate u valence organic group；U indicates 2 to 6 integer.
Work as R1c、R2cWhen for alkyl, which can be straight-chain or branch's chain state, preferably straight-chain.Work as R1c、R2cFor alkane When base, as the carbon number of the alkyl, preferably 1 to 4, particularly good is 1 or 2, more preferably 1.As R1c、R2cCombination, preferably one Person is hydrogen atom, another one is alkyl, it is particularly good be one be hydrogen atom, another one is methyl.
Work as R3cWhen to stretch alkyl, it can be straight-chain or branch's chain state, preferably straight-chain that this, which stretches alkyl,.Work as R3cTo stretch alkane When base, the carbon number of alkyl, preferably 1 to 10, more preferably 1 to 5 are stretched as this, particularly good is 1 or 2, most preferably 1.
R4cDefined u valence organic group, specifically 2 to 6 valence fatty groups to may include atom other than carbon.Make For R4cAtom other than the carbon that may include can enumerate nitrogen-atoms, oxygen atom, sulphur atom, fluorine atom, chlorine atom, bromine atom and iodine Atom etc..R4cThe structure of affiliated fatty group can be straight-chain, branch's chain state or ring-type, can also be composed for these structures Structure.
In the mercaptan compound (E) as shown in formula (E-1), more preferably by following formula (E-2) compound represented:
In formula (E-2), R4c, the definition of u it is identical as formula (E-1), R5cThe alkyl for being 1 to 4 for hydrogen atom or carbon number.
The concrete example of mercaptan compound (E) can enumerate following formula (E-3)~formula (E-16) concrete example, but be not limited to this A little concrete examples:
Total usage amount based on resin (A) is 100 parts by weight, and the content of mercaptan compound (E) is 0.3 parts by weight to 3 weights Measure part, preferably 0.4 parts by weight to 2.8 parts by weight, more preferably 0.5 parts by weight to 2.5 parts by weight.
When chemical amplification positive photosensitive resin composition includes mercaptan compound (E), chemical amplification positive sense The sensitivity of photosensitiveness resin combination is preferable.
Anthracene compound (F)
Anthracene compound (F) can enumerate following concrete example, but be not restricted to these concrete examples: anthracene (anthracene), 9,10- dibutoxy anthracenes, 9,10- dimethoxy anthracene, 2-ethyl-9,10-dimethoxypyrene, 2- third butyl -9,10- dimethoxy Base anthracene, 2,3- dimethyl -9,10- dimethoxy anthracene, 9- methoxyl group -10- methyl anthracene, 9,10- diethoxy anthracene, ethyl -9 2-, 10- diethoxy anthracene, 2- third butyl -9,10- diethoxy anthracene, 2,3- dimethyl -9,10- diethoxy anthracene, 9- ethyoxyl - 10- methyl anthracene, 9,10- dipropoxy anthracene, 9,10- diisopropoxy anthracene, 2- ethyl -9,10- dipropoxy anthracene, 2- third fourth Base -9,10- dipropoxy anthracene, 2,3- dimethyl -9,10- dipropoxy anthracene, 9- isopropoxy -10- methyl anthracene, 9,10- diformazan Phenoxy group anthracene, 2- ethyl -9,10- xylyloxy anthracene, 2- third butyl -9,10- xylyloxy anthracene, dimethyl -9 2,3-, 10- xylyloxy anthracene, 9- toloxyl -10- methyl anthracene, 9,10-, bis--Alpha-Methyl toloxyl anthracene, 2- ethyl -9,10- bis- - Alpha-Methyl toloxyl anthracene, 2- third butyl -9,10- bis--Alpha-Methyl toloxyl anthracene, 2,3- dimethyl -9,10-, bis--α-first Base toloxyl anthracene, 9- (Alpha-Methyl toloxyl) -10- methyl anthracene, 9,10- diphenylanthrancene, 9- methoxyl group anthracene, 9- ethyoxyl The compounds such as anthracene, 9- methyl anthracene, 9- bromine anthracene, 9- methyl mercapto anthracene, 9- ethylmercapto group anthracene.
Total usage amount based on resin (A) is 100 parts by weight, and the content of anthracene compound (F) is 0.2 parts by weight to 1.5 Parts by weight, preferably 0.25 parts by weight are to 1.3 parts by weight, more preferably 0.3 parts by weight to 1.1 parts by weight.
When in chemical amplification positive photosensitive resin composition including anthracene compound (F), chemical amplification positive The sensitivity of photosensitive resin composition is preferable.
Additive (G)
In chemical amplification positive photosensitive resin composition, as long as not influencing effect of the invention, more can further it wrap Containing additive (G), additive (G) can be used alone one kind or use with it is a variety of, end see depending on actual needs.Illustrate additive below (G) particular content.
In chemical amplification positive photosensitive resin composition, to promote plasticity, it also can further contain polyethylene tree Rouge is as additive (G).As the specific example of polyvinyl resin, polyvinyl chloride, polystyrene, poly- hydroxy benzenes second can be enumerated Alkene, polystyrene formic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, gathers polyvinyl acetate Vinylphenol and these copolymer etc..Polyvinyl resin, based on glass transition temperature it is lower for, preferably polyvinyl methyl ether.
Also, being formed to be promoted using photosensitive resin composition in chemical amplification positive photosensitive resin composition Template and metal substrate followability, also can further contain then auxiliary agent as additive (G).
Furthermore in chemical amplification positive photosensitive resin composition, to promote coating, defoaming, equal levelling etc., also Interfacial agent can further be contained as additive (G).As the specific example of interfacial agent, can enumerate BM-1000, BM-1100 (being BM Chmie corporation), MEGAFACEF142D, MEGAFACE F172, MEGAFACE F173, MEGAFACE F183 (being DIC corporation), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (being Sumitomo 3M corporation), SURFLON S-112, SURFLON S-113, SURFLONS-131, SURFLONS-141, SURFLON S-145 (being Asahi Glass corporation), SH-28PA, SH-190, SH-193, SZ-6032, The commercially available fluorine such as SF-8428 (being Toray Silicone corporation) are interfacial agents, only non-limiting in these.
In addition, in chemical amplification positive photosensitive resin composition, to carry out the deliquescent fine tuning to imaging liquid, also Acid, acid anhydrides or higher boiling solvent can further be contained as additive (G).
As acid and the specific example of acid anhydrides, acetic acid, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid, benzene can be enumerated The monocarboxylic acids class such as formic acid, cinnamic acid；Lactic acid, 2- hydroxybutyric acid, 3-hydroxybutyrate, salicylic acid, m-hydroxybenzoic acid, para hydroxybenzene The hydroxyls list carboxylics such as formic acid, 2- hydroxyl cinnamic acid, 3- hydroxyl cinnamic acid, 4-Hydroxycinnamic Acid, 5- Hydroxy M Phthalic Acid, syringic acid Acids；Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic two Formic acid, terephthalic acid (TPA), 1,2- cyclohexane dicarboxylic acid, 1,2,4- cyclohexanetricarboxylic acids, butane tetracarboxylic acid, trimellitic acid, benzene Equal tetracid, pentamethylene tetrabasic carboxylic acid, butane tetracarboxylic acid, 1, the polybasic carboxylic acids class such as 2,5,8- naphthalene tetracarboxylic acids；Itaconic anhydride, succinic acid Acid anhydride, citraconic anhydride, laurylene succinic anhydride, tricarballylic acid's acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydro are adjacent Phthalate anhydride, humic acid acid anhydride, 1,2,3,4- butane tetracarboxylic acid anhydrides, pentamethylene tetracarboxylic dianhydride, phthalic anhydride, benzene equal four The double trimellitic anhydrides of acid anhydrides, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol, glycerine join trimellitic anhydride Equal acid anhydrides.
Also, the specific example as higher boiling solvent, can enumerate N-METHYLFORMAMIDE, n,N-Dimethylformamide, N- first Yl carboxylic acid anilides, N- methylacetamide, n,N-dimethylacetamide, N- methylpyrrole pyridine ketone, dimethyl sulfoxide, benzyl second Ether, two hexyl ethers, pentanedione, different Buddhist ketone, caproic acid, octanoic acid, 1- octanol, 1 nonyl alcohol, benzyl alcohol, phenylmethyl acetate, benzoic acid Ethyl ester, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propene carbonate, phenyl Sai Lusu acetic acid esters Deng.
Also, to promote sensitivity, also can further make containing sensitizer in chemical amplification positive photosensitive resin composition For additive (G).
The manufacturing method of chemical amplification positive photosensitive resin composition
There is no particular restriction for the manufacturing method of chemical amplification positive photosensitive resin composition, can by it is above-mentioned it is each at Divide and is made with common method mixing, stirring.As device workable when mixing, stirring by above-mentioned each ingredient, can enumerate Dissolving machine, homogenizer, three-roll mill etc..After evenly mixing by above-mentioned each ingredient, also gained mixture can further be utilized Sieve, molecular filter etc. are filtered.
The manufacturing method of substrate with mold
Using above-mentioned chemical amplification positive photosensitive resin composition, in the metal watch of the substrate with metal surface It is formed on face and is not particularly limited as the method for the photoresist pattern of the mold to form electroplating formation body.
As preferable method, it can enumerate and include: layering steps, on the metal surface of the substrate with metal surface, The photo-sensitive resin that lamination is made of above-mentioned chemical amplification positive photosensitive resin composition；Step of exposure, to sense Photosensitive resin layer irradiates actinic ray or radioactive ray；And development step, the photo-sensitive resin after exposure is imaged, and make At the manufacturing method of the substrate with mold of the mold to form electroplating formation body.
It as the substrate for lamination photo-sensitive resin, is not particularly limited, always known person can be used, can illustrate for example electric The substrate of sub- part has been formed on set Wiring pattern person.It is using with metal surface for the substrate Person；As the metal species for constituting metal surface, preferably copper, gold, aluminium, more preferably copper.
Photo-sensitive resin be with such as following manner on substrate.Also that is, by the chemical amplification positive of liquid Photosensitive resin composition is coated on substrate, then the photoresist of desired film thickness is formed by heating removal solvent Layer.The thickness of photo-sensitive resin, as long as can using desired film thickness formed as template photoresist pattern as long as be not particularly limited.Sense The film thickness of photosensitive resin layer is not particularly limited, preferably 10 μm or more, more preferably 1 to 150 μm, and particularly good is 20 to 120 μm, most preferably It is 20 to 100 μm.
As coating method of the photosensitive resin composition on substrate, method of spin coating, slot coated method, roller can be used The methods of rubbing method, screen printing, scattering method.Prebake conditions preferably are carried out to photo-sensitive resin.Prebake conditions are because of sense Type, mix proportions, coating film thickness of each ingredient in photosensitiveness resin combination etc. and it is different, only usually at 70 to 150 DEG C, preferably It is 80 to 140 DEG C and 2 to 60 minutes or so.
To the photo-sensitive resin of such as above-mentioned formation, across the mask of predetermined pattern, it is photochemical selectively to irradiate (exposure) Ray or radioactive ray, such as ultraviolet light or luminous ray that wavelength is 300 to 500nm.
As the line source of radioactive ray, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide can be used Lamp, argon laser etc..Also, radioactive ray include microwave, infrared ray, luminous ray, ultraviolet light, X-ray, gamma-rays, electron beam, matter Beamlet, neutron beam, ion beam etc..Radioactive ray exposure is the film of the composition or photo-sensitive resin because of photosensitive resin composition Thickness is equal and different, such as is 100 to 10000mJ/cm when using extra-high-pressure mercury vapour lamp2.Also, radioactive ray include to make photoacid generator (C) light activated is to generate acid.
After exposure, promote photo-sensitive resin heating the diffusion of acid by using known method, in photonasty tree Exposed part in adipose membrane, makes the alkali-solubility of photo-sensitive resin change.
Secondly, follow existing prior art method to be imaged by the photo-sensitive resin after exposing, and by soluble portion Divide dissolution, removal, and forms set photoresist pattern.At this point, being using alkaline aqueous solution as imaging liquid.
As imaging liquid, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammonium hydroxide, second can be used Amine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl-diethyl-amine, dimethylethanolamine, triethanolamine, tetramethylphosphonihydroxide hydroxide Ammonium, tetraethylammonium hydroxide, pyrroles, piperidines, 1,8- diazabicyclo [5,4,0] -7- hendecene, 1,5- diazabicyclo [4,3, 0] aqueous solution of the bases such as -5- nonane.Also, also the aqueous solution to above-mentioned bases can be added the water solubilitys such as methanol, ethyl alcohol in right amount Aqueous solution made of organic solvent or interfacial agent is used as imaging liquid.
Time of developing be it is different because of the composition of photosensitive resin composition or the film thickness of photo-sensitive resin etc., usually 1 To 30 minutes.Developing method can be any for covering liquid method, infusion process, paddle method, injection visualization method etc..
After imaging, flowing water cleaning in 30 to 90 seconds is carried out, and is subject to drying using air gun or baking oven etc..In this way, i.e. The substrate with mold for having the photoresist pattern as mold on the metal surface of the substrate with metal surface can be manufactured.
The manufacturing method of electroplating formation body
To (the portion removed with imaging liquid, non-photoresist portion being formed by according to the above method in the mold of the substrate with mold Point), by conductors such as plating embedment metals, the electroplating formation body of the class of the connection terminal such as convex block or metal column can be formed. In addition, plating process is not particularly limited, always known various methods can be used.As electroplate liquid, it is especially suitable for using Plate solder, copper plating, gold plating, nickel plating solution.Remaining mold, finally follows common method to be gone using stripper etc. It removes.
According to the above method, that is, being formed can inhibit undercutting, while the photoresist pattern as mold.By using being so made The substrate for having the mold that can inhibit undercutting, the electroplating formation body excellent with the adhesion of substrate can be manufactured.
Embodiment will be enumerated below, and the present invention will be described in detail, but the invention is not limited in disclosed by these embodiments Hold.
Detailed description of the invention
For above and other purpose, feature, advantage and embodiment of the invention can be clearer and more comprehensible, institute's accompanying drawings it is detailed Carefully it is described as follows:
[Fig. 1] is the schematic diagram for measuring the rectangularity of photoresist pattern.
[symbol description]
100: substrate
120: photoresist pattern
122: photoresist portion
124: non-photoresist portion
Lb: bottom width
Lt: top width
Specific embodiment
The preparation of resin (A-1)
Synthesis example A-1-1
Nitrogen inlet, blender, heater, condenser pipe and temperature are set on 1000 milliliters of a volume of four cervical vertebra bottles Meter.Then, the diethylene glycol dimethyl ether of 50 parts by weight is added, and oil bath temperature is warming up to 70 DEG C.Then, by 10 parts by weight By the 3- methacryloxymethyl propylene oxide of formula (a-1-1c) compound represented (referred to as (a1-1-1)), 3 parts by weight The methacrylic acid benzene of the methacrylic acids (referred to as (a1-3-1)) of (referred to as (a1-2-1)), 15 parts by weight, 60 parts by weight Ester (referred to as (a1-3-3)), the methacrylic acid third butyl ester (referred to as (a1-3-6)) of 12 parts by weight and 3.5 parts by weight Double -2- the methylbutyronitriles (referred to as AMBN) of 2,2 '-azos be added in four cervical vertebra bottles, and be slowly stirred above-mentioned mixed solution.It is whole The reaction temperature of a polymerization process maintains 70 DEG C, and polymerization time continues 6 hours, after the completion of polymerization, by polymerizate from four necks It is taken out in conical flask, and solvent is sloughed, resin (A-1-1) can be obtained.
Synthesis example A-1-2 to synthesis example A-1-11
Synthesis example A-1-2 to A-1-11 is to prepare resin (A-1-2) to (A- with the step identical as synthesis example A-1-1 1-11), different places is: change reaction temperature, the reaction time, composition type and usage amount, and state in detail in table 1.
The preparation of resin (A-2)
Synthesis example A-2-1
Nitrogen inlet, blender, heater, condenser pipe and temperature are set on 1000 milliliters of a volume of four cervical vertebra bottles Meter.Then, the diethylene glycol dimethyl ether of 50 parts by weight is added, and oil bath temperature is warming up to 70 DEG C.Then, by 5 parts by weight Acrylic acid (ethyl-diethylene glycol) ester (referred to as (a2-1-1)), 15 parts by weight methacrylic acid (referred to as (a2-3-1)), 2- methyl -2- Adamantylmethyl the propylene of the phenyl methacrylates (referred to as (a2-3-3)) of 60 parts by weight, 20 parts by weight Four necks are added in acid esters (referred to as (a2-3-5)) and the double -2- methylbutyronitriles (referred to as AMBN) of 2,2 '-azos of 3.5 parts by weight In conical flask, and it is slowly stirred above-mentioned mixed solution.The reaction temperature of entire polymerization process maintains 70 DEG C, and polymerization time continues 6 Hour, after the completion of polymerization, polymerizate is taken out, and solvent is sloughed from four cervical vertebra bottles, resin (A-2-1) can be obtained.
Synthesis example A-2-2 to A-2-15
Synthesis example A-2-2 to A-2-15 is to prepare resin (A-2-2) to (A- with the step identical as synthesis example A-2-1 2-15), different places is: change reaction temperature, the reaction time, composition type and usage amount, and state in detail in table 2.
The preparation of novolac resin (B)
Synthesis example B-1
Nitrogen inlet, blender, heater, condenser pipe and temperature are set on 1000 milliliters of a volume of four cervical vertebra bottles Meter, import nitrogen after add 0.40 mole of m-cresol, 0.50 mole of p-Cresol, 0.10 mole of 3,4-Xylenol, 0.65 mole of formaldehyde and 0.2 mole of oxalic acid.Being slowly stirred makes reaction solution be warming up to 100 DEG C, and gathers at this temperature Condensation 6 hours.Then, reaction solution is warming up to 180 DEG C, and is dried under reduced pressure with the pressure of 10mmHg, by solvent devolatilization After can obtain novolac resin (B-1).
Synthesis example B-2 to synthesis example B-6
Synthesis example B-2 to synthesis example B-6 is to prepare novolac resin (B-2) with the step identical as synthesis example B-1 To (B-6), different places is: change reaction temperature, the reaction time, composition type and usage amount, and state in detail in table 3.
The preparation of chemical amplification positive photosensitive resin composition
Embodiment 1
By the resin (A-1-1) of resulting 50 parts by weight of aforementioned synthesis example, the resin (A-2-1) of 50 parts by weight, 20 weight The third of 60 parts by weight is added in the novolac resin (B-1) and 0.5 parts by weight photoacid generator C-1 (hereinafter referred to as C-1) of part After glycol methyl ether acetate (hereinafter referred to as D-1), with swing-out stirrer, dissolved mixing, i.e., it is modulated and chemical increasing Width type positive-type photosensitive resin composition, the chemical amplification positive photosensitive resin composition is with following each evaluation of measuring Mode is evaluated, and acquired results are as shown in table 4.
Embodiment 2 is to embodiment 25
Embodiment 2 to embodiment 25 is made using with the chemical amplification positive photosensitive resin composition of embodiment 1 The identical operating method of method, the difference is that embodiment 2 to embodiment 25 is to change chemical amplification positive photonasty tree The type and usage amount of raw material in fat composition, formula and following evaluation result are as shown in table 4.
Comparative example 1 is to comparative example 9
Comparative example 1 to comparative example 9 is using the chemical amplification positive photosensitive resin composition production side with embodiment 1 The identical operating method of method, the difference is that comparative example 1 to comparative example 9 is to change chemical amplification positive photoresist group At the type and usage amount of raw material in object, formula and following evaluation result are as shown in table 5.
Evaluation method
1. sensitivity:
By the chemical amplification positive photosensitive resin composition of Examples and Comparative Examples, it is coated on using spin coater On copper base when 6,50 μm of film thickness of photo-sensitive resin is formed.Thereafter, the photo-sensitive resin is carried out at 110 DEG C 6 minutes prebake conditions.Mask and (the Ultratech company of exposure device Titan 2 after prebake conditions, using the sectional hole patterns of 60 μm of diameters System), pattern exposure is carried out with g line, h line and i line and periodically changes light exposure.Then, by substrate-placing in heating plate On, (PEB) is heated after exposure in 3 minutes is carried out at 100 DEG C.Thereafter, it drips 2.38% hydroxide four to photo-sensitive resin First ammonium (TMAH) aqueous solution is placed 60 seconds at 23 DEG C, is repeated 4 times and is imaged.Thereafter, flowing water cleaning is carried out, then is blown It spills nitrogen and obtains the thick film photoresist pattern of the contact hole pattern with 50 μm of diameters.
◎: light exposure < 100mJ/cm2
Zero: 100mJ/cm2≤ light exposure < 150mJ/cm2
Δ: 150mJ/cm2≤ light exposure < 200mJ/cm2
×: light exposure >=200mJ/cm2。
2. rectangularity:
Fig. 1 is please referred to, Fig. 1 is the schematic diagram for measuring the rectangularity of photoresist pattern.It is coated on the photoresist of substrate 100 Layer forms the photoresist pattern 120 with photoresist portion 122 and non-photoresist portion 124 after above-mentioned exposure, development step.For upper The section configuration for stating the photoresist pattern of optimum exposure is observed, and bottom width Lb and the top in non-photoresist portion 124 are measured The value of width Lt, and calculate index of the Lt/Lb value as rectangularity.Evaluation criterion is as follows:
◎: 0.9 < Lt/Lb< 1.1
Zero: 0.85 < Lt/Lb≤ 0.9 or 1.1≤Lt/Lb< 1.15
Δ: 0.75 < Lt/Lb≤ 0.85 or 1.15≤Lt/Lb< 1.25
×: Lt/Lb< 0.75 or Lt/Lb> 1.25.
As shown in table 4, when the resin (A-1) and resin for being used to synthesize chemical amplification positive photosensitive resin composition (A-2) when mixture contains specific monomer (a-1-1), monomer (a-1-2) and monomer (a-2-1) respectively, chemical amplification type is just The sensitivity of type photosensitive resin composition is good, and is formed by photoresist pattern also and has good rectangularity.Furthermore, when The mixture of synthetic resin (A-2), which contains monomer (a-2-2) and/or resin (A-1) and resin (A-2), has specific amount ranges When, it can more improve the rectangularity that chemical amplification positive photosensitive resin composition is formed by photoresist pattern.And in constituent Anthracene compound (F) is used using in mercaptan compound (E) and/or constituent, can further improve the sensitivity of constituent.
On the other hand, as shown in table 5, if being used to synthesize the resin of chemical amplification positive photosensitive resin composition (A-1) and the mixture of resin (A-2) does not contain specific monomer (a-1-1), monomer (a-1-2) and monomer (a-2-1), then chemical The sensitivity of amplification positive photosensitive resin composition is bad and to be formed by the rectangularity of photoresist pattern poor.
The above described is only a preferred embodiment of the present invention, limitation in any form not is done to the present invention, though So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this profession Member, without departing from the scope of the present invention, when the technology contents using the disclosure above are modified or are modified For the equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, according to the technical essence of the invention Any simple modification, equivalent change and modification made to the above embodiment, all of which are still within the scope of the technical scheme of the invention.
Table 4
Table 5

Claims (13)

1. a kind of chemical amplification positive photosensitive resin composition characterized by comprising
Resin (A) includes resin (A-1) and resin (A-2)；
Novolac resin (B)；
Photoacid generator (C)；And
Solvent (D),
Wherein the resin (A-1) is to be reacted by one first mixture and obtained, which includes monomer (a-1-1) and monomer (a-1-2),
The monomer (a-1-1) contains the structure such as formula (a-1-1a):
In formula (a-1-1a), R1aFor hydrogen atom or methyl, R2aFor low alkyl group and X3aIt is common with the carbon atom that is bonded Form the hydrocarbon ring of carbon number 5 to 20；And
The monomer (a-1-2) contains cyclic ether group, and
Wherein, which is to be reacted by one second mixture and obtained, which includes monomer (a-2-1), and should Monomer (a-2-1) stretches alkyl chain containing polyoxy.
2. chemical amplification positive photosensitive resin composition according to claim 1, which is characterized in that second mixing Object includes monomer (a-2-2), which contains the structural formula such as formula (a-2-2a):
In the formula (a-2-2a), R1bIt is respectively independent to indicate hydrogen atom ,-CH3、-CF3Or-CH2OH；R2bIndicate alkyl, naphthenic base Or aryl；R3bTo R12bThe respectively independent alkyl for indicating hydrogen atom or contain or do not contain heteroatomic 1 valence, or formed mutually Ring, wherein when forming ring mutually, R3bTo R12bExpression contains or does not contain heteroatomic divalent alkyl；R3bTo R12bIndicate bond It can not be bonded each other between any object in adjacent carbon person, can also form double bond；T indicates the linker of singly-bound or divalent；The T The divalent linker be stretch alkyl ,-COO-RtBase ,-O-RtBase, and RtAlkyl is stretched to stretch alkyl or ring.
3. chemical amplification positive photosensitive resin composition according to claim 1, which is characterized in that further include mercaptan Compound (E), the mercaptan compound (E) have structure shown in following formula (E-1):
In the formula (E-1), R1c、R2cThe respectively independent alkyl for indicating that hydrogen atom or carbon number are 1 to 4, R3cIndicate singly-bound or carbon number For 1 to 10 alkyl of stretching, R4cIndicate u valence organic group；U indicates 2 to 6 integer.
4. chemical amplification positive photosensitive resin composition according to claim 1, which is characterized in that further include anthracene class Compound (F).
5. chemical amplification positive photosensitive resin composition according to claim 1, which is characterized in that be based on the resin (A) total usage amount is 100 parts by weight, and the content of the novolac resin (B) is 20 parts by weight to 180 parts by weight, light acid The content of producing agent (C) is 0.5 parts by weight to 4.5 parts by weight, and the content of the solvent (D) is 60 parts by weight to 800 parts by weight.
6. chemical amplification positive photosensitive resin composition according to claim 1, which is characterized in that be based on the resin (A) total usage amount is 100 parts by weight, and the content of the resin (A-1) is 60 parts by weight to 90 parts by weight, and the resin (A-2) Content be 10 parts by weight to 40 parts by weight.
7. chemical amplification positive photosensitive resin composition according to claim 1, which is characterized in that based on this first Total usage amount of mixture is 100 parts by weight, and the content of the monomer (a-1-1) is 10 parts by weight to 50 parts by weight, the monomer (a- Content 1-2) is 3 parts by weight to 20 parts by weight.
8. chemical amplification positive photosensitive resin composition according to claim 1, which is characterized in that based on this second Total usage amount of mixture is 100 parts by weight, and the content of the monomer (a-2-1) is 5 parts by weight to 50 parts by weight.
9. chemical amplification positive photosensitive resin composition according to claim 2, which is characterized in that based on this second Total usage amount of mixture is 100 parts by weight, and the content of the monomer (a-2-2) is 3 parts by weight to 20 parts by weight.
10. chemical amplification positive photosensitive resin composition according to claim 3, which is characterized in that be based on the tree Total usage amount of rouge (A) is 100 parts by weight, and the content of the mercaptan compound (E) is 0.3 parts by weight to 3 parts by weight.
11. chemical amplification positive photosensitive resin composition according to claim 4, which is characterized in that be based on the tree Total usage amount of rouge (A) is 100 parts by weight, and the content of the anthracene compound (F) is 0.2 parts by weight to 1.5 parts by weight.
12. a kind of manufacturing method of the substrate with mold characterized by comprising
Layering steps, on the metal surface of the substrate with metal surface, lamination is by such as claim 1 to claim 11 Any one of described in the photo-sensitive resin that is constituted of chemical amplification positive photosensitive resin composition；
Step of exposure irradiates active ray or radioactive ray to the photo-sensitive resin；And
Development step develops to the photo-sensitive resin after exposure, and is made the mold to form electroplating formation body.
13. a kind of manufacturing method of electroplating formation body characterized by comprising
It is real to the substrate manufactured by the manufacturing method by the substrate as claimed in claim 12 with mold with mold Plating is applied, and the step of electroplating formation body is formed in the mold.
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